Hydrotreating catalyst comprising an interstratified crystalline clay-type aluminosilicate component and a crystalline zeolitic molecular sieve component and process using said catalyst

ABSTRACT

A catalyst comprising an interstratified synthetic crystalline aluminosilicate cracking component and a crystalline zeolitic molecular sieve component, which may be dispersed in a matrix comprising a siliceous gel, if desired one or both of said components being substantially in the ammonium or hydrogen form and substantially free of any catalytic metal or metals when dispersed in a matrix, and if desired one of said components being substantially in the ammonium or hydrogen form and substantially free of any catalytic metal or metals when not dispersed in a matrix, a hydrogenating component selected from platinum and compounds thereof and palladium and compounds thereof, a component selected from the metals cerium, manganese, zinc, and compounds of said metals, and processes using said catalyst.

Unite States atent 1191 Csicsery et al.

HYDROTREATING CATALYST COMPRISING AN INTERSTRATIFIED CRYSTALLINE CLAY-TYPE ALUMINOSILICATE COMPONENT AND A CRYSTALLINE ZEOLITIC MOLECULAR SIEVE COMPONENT AND PROCESS USING SAID CATALYST Inventors: Sigmund M. Csicsery, Lafayette; James R. Kittrell, Palos Verdes Estates, both of Calif.

Chevron Research Company, San Francisco, Calif.

Filed: Jan. 30, 1970 Appl. No.: 7,179

Assignee:

References Cited UNITED STATES PATENTS l0/l970 .Iaffe ..252/455 X 3,558,473 l/l97l Csicsery et a] ..252/455 X 3,304,254 2/1967 Eastwood et al. ..208/l l 1 3,535,231 10/1970 Kittrell ..252/455 X Primary ExaminerC. F. Dees Attorney-J. D. Foster, G. F. Magdeburger, Roy H. Davies and J. A. Buchanan, Jr.

[5 7 ABSTRACT A catalyst comprising an interstratified synthetic crystalline aluminosilicate cracking component and a crystalline zeolitic molecular sieve component, which may be dispersed in a matrix comprising a siliceous gel, if desired one or both of said components being substantially in the ammonium or hydrogen form and substantially free of any catalytic metal or metals when dispersed in a matrix, and if desired one of said components being substantially in the ammonium or hydrogen form and substantially free of any catalytic metal or metals when not dispersed in a matrix, a hydrogenating component selected from platinum and compounds thereof and palladium and compounds thereof, a component selected from the metals cerium, manganese, zinc, and compounds of said metals, and processes using said catalyst.

20 Claims, 2 Drawing Figures IIYDROTREATING CATALYST COMPRISING AN INTERSTRATIFIED CRYSTALLINE CLAY-TYPE ALUMINOSILICATE COMPONENT AND A CRYSTALLINE ZEOLITIC MOLECULAR SIEVE COMPONENT AND PROCESS USING SAID CATALYST INTRODUCTION This invention relates to catalytic hydrocracking of petroleum distillates and solvent-deasphalted residua 1 to produce high-value fuel products, including jet fuels and gasoline.

PRIOR ART It is known that a catalyst may comprise a crystalline zeolitic molecular sieve component associated with other catalyst components. It is also known that at least some of said other catalyst components may be in the form of a matrix in which the molecular sieve component is dispersed. It is also known that such catalysts may be used for such reactions as catalytic cracking, hydrocracking, and hydrodesulfurization. Representative prior art patents disclosing one or more of the foregoing matters include:-

U.S. Pat. No. 3,140,25l

US. Pat. No. 3,140,253

British Patent No. 1,056,301

French Patent No. 1,503,063

French Patent No. 1,506,793

There has been a continuing search for further improvements in such catalysts, and in similar multicomponent catalysts, particularly for hydrocracking and hydrofining uses.

A crystalline zeolitic molecular sieve cracking component, while relatively insensitive to organic nitrogen compounds and ammonia,- has a well-ordered and uniform pore structure as a result of the crystal structure having bonds that are substantially equally strong in three dimensions. This provides definite limitations on the access of reactant molecules to the interiors of the pores. Further, most catalysts containing crystalline zeolitic molecular sieve components cause cracking, for example hydrocracking, to occur in a manner that results in high yields of gasoline but relatively poor yields of middle distillates such as jet fuels.

Accordingly, it would be reasonable to expect that when middle distillates, for example jet fuels, are the desired primary product of a hydrocracking process, a catalyst not containing a molecular sieve cracking component should be selected.

One class of materials that could be considered as a cracking component of a hydrocracking catalyst in lieu of a crystalline zeolitic molecular sieve comprises the clays, or phyllosilicates, which are clay-type aluminosilicates. These materials are crystalline in form and, contrary to the crystalline zeolitic molecular sieves, have pores elongated in two directions. Some of these materials have the ability to expand upon the addition of a liquid. Some of them have cracking activity, or can be activated, as by acid treatment, to impart cracking activity to them. Natural clays have differing properties and combinations of properties, for example:

Cracking activity, Expandableor can be activated D. Illite E. Chlorite F. vermiculite G. Attapulgas Natural clays can be complex combinations from more than one category in the above list. For example, they can comprise an expandable component and a non-expandable component, a component with good cracking activity and one having relatively low 0 cracking activity, etc.

Synthetic clays also can be produced which are analogous to natural clays in the above categories, and synthetic clays also can be complex combinations from more than one category in the above list.

It is impossible to predict with any reasonable accuracy which natural or synthetic clays in the many possible categories and combinations of categories will be operable as a component of a hydrocracking catalyst to produce various possible desired results. If the hydrocracking result desired is the production of high yields of jet fuel, one skilled in the art reasonably could conclude that he should select a catalyst not containing a crystalline zeolitic molecular sieve cracking component. However, he is left with an extensive array of other choices, including amorphous silica-alumina gels, treated and untreated natural clays in many categories, treated and untreated synthetic clays in many categories, etc. Assuming that one skilled in the art would choose to reject amorphous silica-alumina as the only cracking component in the desired catalyst, and would choose to try to make a catalyst containing a natural or synthetic clay that would produce high yields of jet fuel, he would find that some of the clays have activity that is far too low to be acceptable. He also would find that hydrocracking catalysts that contained some clays that might have acceptable activities would have poor stabilities if they contained certain hydrogenating components or combinations thereof. That is, he would find that such catalysts would lose their activities at an unacceptably fast rate during hydrocracking service.

In view of the foregoing, it would be desirable if a hydrocracking catalyst were available that contained a clay-type cracking component with high activity capable of cracking a hydrocarbon feedstock to produce a total liquid product containing a high proportion of jet fuel boiling range materials. It would also be desirable for such a catalyst to have a high stability, that is, a low fouling rate in hydrocracking service. It further would be desirable if such a catalyst had a high degree of tolerance for organic nitrogen compounds in the feedstock, and if it could be tailored, by adjustment of proportions of various components thereof, to produce middle distillates, particularly jet fuels, and gasolines in different ratios.

OBJECTS Accordingly, objects of the present invention include providing an improved hydrocracking catalyst containing a clay-type cracking component that has, compared with similar prior art catalysts:

1. high hydrocracking activity;

2. improved hydrocracking selectivity, particularly for the production of middle distillates, including jet fuels;

3. high nitrogen tolerance;

4. high hydrocracking stability;

5. improved amenability to being tailored, by adjustment of the ratio of different components, to produce middle distillates, particularly jet fuels, and gasolines in different ratios.

Further objects of the present invention include provision of a hydrocracking process using said improved catalyst, that is capable of producing excellentquality jet fuel and other valuable fuel products.

The present invention will best be understood, and further objects and advantages thereof will be apparent, from the following description when read in connection with the accompanying drawing.

DRAWING In the drawing,

FIG. 1 is a diagrammatic illustration of apparatus and flow paths suitable for carrying out the process of several of the embodiments of the present invention, wherein the catalyst of the present invention is used on a once-through basis to hydrocrack a hydrocarbon feedstock to produce more valuable products, some of which may be further upgraded by catalytic reforming or catalytic hydrocracking, if desired.

FIG. 2 is a diagrammatic illustration of apparatus and flow paths suitable for carrying out the process of additional embodiments of the present invention, wherein the catalyst of the present invention is used to hydrocrack a hydrocarbon feedstock, wherein the hydrocracking zone may be operated on a recycle basis, and wherein certain portions of the effluent from the hydrocracking zone may be catalytically reformed or catalytically cracked, as desired.

STATEMENT OF INVENTION In accordance with the present invention, it has been found that (a) for producing high hydrocracking yields of middle distillates, particularly jet fuels, with a hydrocracking catalyst containing a clay-type cracking component, and (b) for maintaining high catalyst stability during hydrocracking service, unexpectedly good results are obtained with a hydrocracking catalyst that:

1. contains a crystalline clay cracking component of a very specific type, namely one which a. is a synthetic crystalline aluminosilicate,

b. is in the form of interstratified materials, or materials in mixed layers, said materials being clays from two different clay categories, namely the smectite and illite categories,

c. has an alkali metal cation content in the range -0.5 wt. on an anhydrous clay basis,

d. has a content of fluorine, in combined form, in the range 0-3 wt. preferably 0-2.S wt. and more preferably 0.52.5 wt. on an anhydrous clay basis;

2. contains a crystalline zeolitic molecular sieve cracking component; and

3. contains a hydrogenating component selected from platinum and compounds thereof and palladium and compounds thereof; and

4. contains a promoter component selected from the metals cerium, manganese, zinc, and compounds of said metals.

Said crystalline clay cracking component containing mixed layers of clays from the smectite and illite categories may be, for example, prior to drying and calcining the catalyst in which it is contained, a randomly interstratified synthetic montmorillinite-mica mineral of the type described in Granquist US. Pat. No.

3,252,757. The synthetic mineral described in that patent has the empirical formula "Slog I A1203 I zxHgo,

where the layer lattices comprise said silica, said alumina, and said B, and where n is from 2.4 to 3.0

m is from 0.2 to 0.6

A is one equivalent of an exchangeable cation having a valence not greater than 2, and is external to the lattice,

is chosen from the group of negative ions which consists of F, OH, /2O and mixtures thereof, and is internal in the lattice, and

x is from 2.0 to 3.5 at 50 percent relative humidity, said mineral being characterized by a d spacing at said humidity within the range which extends from a lower limit of about 10.4 A. to an upper limit of about 12.0 A. when A is monovalent, to about 14.7 A. when A is divalent, and to a value intermediate between 12.0 A. and 14.7 A. when A includes both monovalent and divalent cations. The equivalent of an exchangeable cation, A, in said mineral may be chosen from the group consisting of 14*, NH,*, Li K, wCa kMg /Sr %Ba and mixtures thereof. Said synthetic mineral is known from U.S. Pat. No. 3,252,889 to have application in the dried and calcined form as a component of a catalytic cracking catalyst, and applications of said synthetic mineral in the dried and calcined form as a component of a hydrocracking catalyst have been disclosed in my copending application for Hydrotreating Catalyst and Process, filed Aug. 5, 1968. By dried and calcined form is meant the mineral form resulting from drying and calcining the catalyst in which it is contained, which form may be different from the form of the mineral defined by the foregoing formula.

When the catalyst of the present invention does not comprise a matrix, as discussed below, one of said crystalline cracking components may be substantially in the ammonium or hydrogen form and may be substantially free of any catalytic loading metal or metals.

In particular embodiments, the catalyst of the present invention further comprises a matrix comprising a siliceous gel and said hydrogenating component, and said crystalline clay component and said crystalline molecular sieve component are in particulate form and are dispersed through said matrix. At least one of saidv crystalline components may be substantially in the ammonium or hydrogen form and may be substantially free of any catalytic loading metal or metals.

A particular embodiment of the catalyst of the present invention is a catalyst comprising:

a. a gel matrix comprising a silica-alumina gel,

b. a hydrogenating component, which may be located in said matrix, selected from platinum and compounds thereof and palladium and compounds thereof,

c. a component, which may be located in said matrix, selected from the metals cerium, manganese, zinc, and compounds of said metals.

d. an interstratified smectite-illite aluminosilicate component in particulate form, and

e. a crystalline zeolitic molecular sieve in particulate form; said interstratified aluminosilicate component and said molecular sieve component being dispersed through said gel matrix. Preferably, the catalyst of the present invention will be further characterized by an average pore diameter below 100 Angstroms and a surface area about 200 square meters per gram, when it includes a matrix comprising a silica-alumina gel.

The catalyst of the present invention, whether or not it includes a matrix comprising a silica-alumina gel, further may comprise a component selected from the metals Ag, Cu, Sn, Ti, Zr, Th, Hf, V, alkaline earth metals Mg, Ca, Sr and Ba, rare earth metals having atomic numbers 57 and 59-71, and compounds of said metals. When said catalyst includes a matrix comprisin g a silica-alumina gel, said component may be present in said matrix in an amount of 0.1 to weight percent, preferably 0.5 to 9 weight percent, of said matrix, calculated as metal.

When said catalyst does not include a matrix comprising a silica-alumina gel, said component comprising platinum or palladium may be present therein in an amount of 0.01 to 3 weight percent, preferably 0.01 to 1 weight percent, calculated as metal and based on the total of said interstratified aluminosilicate and crystalline zeolitic molecular sieve components. When said catalyst includes a matrix comprising a silica-alumina gel, said component comprising platinum or palladium may be present therein in an amount of 0.01 to 3 weight percent, preferably 0.01 to 1 weight percent, calculated as metal and based on said matrix.

When said catalyst does not include a matrix comprising a silica-alumina gel, said component comprising cerium, manganese or zinc may be present therein in an amount of 0.l to weight percent, preferably 0.5 to 10 weight percent, calculated as metal and based on the total of said interstratified aluminosilicate and crystalline zeolitic molecular sieve components. When said'catalyst includes a matrix comprising a silica-alumina gel, said component comprising cerium, manganese or zinc may be present therein in an amount of 0.1 to weight percent, preferably 0.5 to 20 weight percent, calculated as metal and based on said matrix.

Said catalyst advantageously may contain tin or a compound thereof, regardless of whether said catalyst includes a matrix comprising a silica-alumina gel. The tin or compound thereof may be present in said catalyst in an amount of 0.5 to weight percent, preferably 2 to 15 weight percent, based on the total catalyst and calculated as metal, when said catalyst includes a matrix comprising a silica-alumina gel. When said catalyst does not include a matrix comprising a silicaalumina gel, the tin or compound thereof may be present in an amount of 0.2 to 15 weight percent, based on the total catalyst and calculated as metal. When tin or a compound thereof is present, both the hydrocracking activity and the hydrogenation activity of said catalyst are higher, compared with the same catalyst with no tin or tin compound present. Further, when tin or a compound thereof is present, the hydrogenation activity of the catalyst can be controlled in an essentially reversible manner by varying the amount of sulfur present in the hydrocarbon feed.

Said interstratified aluminosilicate is present in said catalyst in an amount of 5 to 99 weight percent of said composite. Said crystalline zeolitic molecular sieve component is present in said catalyst in an amount of l to weight percent, based on the total catalyst. At higher ratios of interstratified aluminosilicate to molecular sieve, higher ratios of middle distillates to gasoline will be produced, and vice versa.

Another particular embodiment of the catalyst of the present invention is a catalyst comprising:

A. A gel matrix comprising:

a. 5 to weight percent, preferably 15 to 70 weight percent, silica,

b. 10 to 94 weight percent, preferably 30 to 85 weight percent, alumina,

c. a platinum or palladium component in the form of metal, oxide, sulfide or any combination thereof, in an amount of 0.01 to 3 weight percent, preferably 0.01 to 1 weight percent, of said matrix, calculated as metal,

(1. a cerium, manganese or zinc component, in the form of metal, oxide, sulfide or any combination thereof, in an amount of 0.1 to 25 weight percent, preferably 0.5 to 20 weight percent, of said matrix, calculated as metal;

B. An interstratified smectite-illite aluminosilicate (which may be substantially in the ammonium or hydrogen form, substantially free of any catalytic loading metal or metals), said interstratified aluminosilicate further being in particulate form and being dispersed through said matrix;

C. A crystalline zeolitic molecular sieve (which may be substantially in the ammonium or hydrogen form, substantially free of any catalytic loading metal or metals), said molecular sieve further being in particulate form and being dispersed through said matrix.

Another particular embodiment of the catalyst of the present invention is a catalyst consisting essentially of:

A. A porous xerogel comprising:

a. 5 to 85 weight percent, preferably 15 to 70 weight percent, silica,

b. l0 to 94 weight percent, preferably 30 to 85 weight percent, alumina,

c. palladium, in the form of metal, oxide, sulfide or any combination thereof, in an amount of 0.01

to 3 weight percent, preferably 0.01 to 1 weight percent, of said xerogel, calculated as metal,

. cerium, manganese or zinc, in the form of metal, oxide, sulfide or any combination thereof, in an amount of 5 to 25 weight percent, preferably 10 to 20 weight percent, of said xerogel, calculated as metal,

e. titanium oxide, in an amount of l to 10 weight percent, preferably 5 to 9 weight percent, of said xerogel, calculated as metal;

. An interstratified smectite-illite aluminosilicate, in an amount of 5 to 99 weight percent of said catalyst, said interstratified aluminosilicate preferably being substantially in the ammonium or hydrogen form, and preferably being substantially free of any catalytic loading metal or metals, said interstratified aluminosilicate further being in the form of particles, said particles being dispersed through said xerogel;

C. A crystalline zeolitic molecular sieve, in an amount of l to 70 weight percent of said catalyst, said molecular sieve preferably being substantially in the ammonium or hydrogen form, and preferably being substantially free of any catalytic loading metal or metals, said molecular sieve further being in the form of particles, said particles being dispersed through said xerogel; said catalyst having an average pore diameter below 100 Angstroms and a surface area above 200 square meters per gram.

Still further in accordance with the present invention, there is provided a hydrotreating process which comprises contacting a hydrocarbon feed containing substantial amounts of materials boiling above 200F. and selected from the group consisting of petroleum distillates, solvent-deasphalted petroleum residua, shale oils and coal tar distillates, in a reaction zone with hydrogen and the catalyst described above, at hydrotreating conditions including a temperature in the range 400 to 950F., a pressure in the range 800 to 3,500 psig, a liquid hourly space velocity in the range 0.1 to 5.0 and a total hydrogen supply rate of 200 to 20,000 SCF of hydrogen per barrel of feedstock, and recovering hydrotreatcd products from said reaction -zone. The hydrocarbon feed may contain a substantial amount of organic nitrogen, because the catalyst of the present invention is extremely tolerant of organic nitrogen as well as of ammonia. The catalyst is an efficient hydrodenitrification catalyst, will accomplish hydrodenitrification and hydrocracking concurrently and efficiently, and may be used as a hydrodenitrification catalyst in a zone preceding a hydrocracking zone containing a similar or different hydrocracking catalyst. A superior jet fuel product may be produced when the catalyst is used for hydrocracking a suitable feedstock. A superior feedstock for a catalytic reformer also may be produced when the catalyst is used for hydrocracking. The hydrocracking zone effluent boiling above the gasoline boiling range, or boiling above the jet fuel boiling range when a jet fuel product is being recovered, may be catalytically cracked to produce. additional valuable products.

The reference to an interstratified aluminosilicate component or a molecular sieve component substantially free of any catalytic loading metal or metals means that the component-in question contains less than 0.1 weight percent noble metals, and less than 0.5 weight percent of total catalytic metal or metals, based on that component. The catalytic metal or metals include tin, platinum and palladium. If desired, the interstratified aluminosilicate component or the molecular sieve component, or both, may be loaded with 0.1 to 10 weight percent, based on said interstratified aluminosilicate and/or molecular sieve component or components, of a polyvalent, non-catalytic ion selected from Ti, Zr, Hf, Th, rare earths having atomic numbers 57 and 59-71, and alkaline earths Mg, Ca, Sr and Ba, while still keeping the component so loaded substantially free of any catalytic loading metal or metals.

.It will be noted that the weight ratio of catalytic metal in the matrix portion of the catalyst to catalytic metal in the interstratified aluminosilicate and molecular sieve portions of the catalyst is high, in the catalyst embodiments which include a matrix comprising a silica-alumina gel, in which is dispersed an interstratified aluminosilicate substantially free of any catalytic loading metal or metals and a molecular sieve substantially free of any catalytic loading metal or metals.

In addition to the 0-3 wt. fluorine content of the crystalline clay cracking component of the catalyst of the present invention, other catalyst components present also may contain fluorine, in combined form, in an amount of 0-5 wt. of said other components. For example, when the catalyst comprises a gel matrix, said matrix may contain 0-5 wt. combined fluorine. The fluorine may be incorporated into the catalyst in any convenient manner that will result in a substantially uniform distribution of combined fluorine on or through the other catalyst components. A preferred manner of incorporating the fluorine in the catalyst is by the addition of a soluble fluoride compound, for example sodium fluoride, ammonium fluoride, ammonium bifluoride or hydrofluoric acid. The fluoride compound may be combined with the other catalyst components at any of various stages of catalyst preparation. When the catalyst includes a matrix comprising a siliceous gel, the fluoride compound may be formed with the matrix as a component thereof.

HYDROCARBON FEEDSTOCKS The feedstocks supplied to the hydrocracking zone in the process of the present invention are selected from the group consisting of petroleum distillates, solvent-deasphalted petroleum residua, shale oils and coal tar distillates. The feedstocks contain substantial amounts of materials boiling above 20.0F., preferably substantial amounts of materials boiling in the range 350 to 950F., and more preferably in the range 400 to 900F. Suitable feedstocks include those heavy distillates normally defined as heavy straight-run gas oils and heavy cracked cycle oils, as well as conventional FCC feed and portions thereof. Cracked stocks may be obtained from thermal or catalytic cracking of various stocks, including those obtained from petroleum, gilsonite, shale and coal tar. The feedstocks need not be subjected to a prior hydrofining treatment before being hydrocracked in the process of the present invention, particularly when the catalyst of the present invention comprises a silica-alumina gel matrix. When such an embodiment of the catalyst of the present invention is used, feedstocks may contain as high as several thousand parts per million organic nitrogen (although preferably the organic nitrogen content will be less than 1,000 parts per million organic nitrogen),

and also may contain several weight percent organic sulfur.

CATALYST COMPRISING AN INTERSTRATIFIED ALUMlNOSlLlCATE COMPONENT AND A- MOLECULAR SIEVE COMPONENT, AND PREPARATION THEREOF A. General The interstratified aluminosilicate used in preparing the hydrocracking catalyst may be any synthetic catalytically active interstratified smectite-illite aluminosilicate, although the synthetic interstratified aluminosilicate of Granquist U.S. Pat. No. 3,252,757 is preferred. The sodium content of the interstratified aluminosilicate should be below 0.5 weight percent, calculated as metal, on an anhydrous interstratified aluminosilicate basis.

The crystalline zeolitic molecular sieve component of the catalyst may be of any type that is known in the art as a useful component of a hydrocracking catalyst. A decationized molecular sieve is preferred. The sodium content of the molecular sieve should be below weight percent, calculated as metal. Especially suitable are faujasite, particularly Y type and X type faujasite, and mordenite, in the ammonium form, hydrogen form, alkaline earth-exchanged form, or rare earth-exchanged form. An ultra-stable form of molecular sieve may be used, that is, one having a sodium content below about 3 weight percent, calculated as Na o, a unit cell size below about 24.65 Angstroms, and a silica/alumina ratio above about 2.15.

B. Method of Preparation When Catalyst Does Not Include a Matrix Comprising a Siliceous Gel When the catalyst does not include a matrix comprising a siliceous gel, the hydrogenating components may be added to the interstratified aluminosilicate and molecular sieve components in any convenient manner, as by impregnation, adsorption or ion exchange, using suitable hydrogenating component precursor compounds, for example nitrates. C. Method of Combining Interstratified Aluminosilicate and Molecular Sieve Components with Matrix When Catalyst Includes a Matrix Comprising a Siliceous Gel When the catalyst includes a matrix comprising a siliceous gel, the interstratified aluminosilicate component and the molecular sieve component may be dispersed therein by cogelation of the matrix around said interstratified aluminosilicate component and said molecular sieve component in a conventional manner.

The desired hydrogenating components may be included in the matrix during preparation thereof, in the form of suitable precursor compounds, for example chlorides.

The interstratified aluminosilicate and molecular sieve components, substantially in the ammonium or hydrogen form, may be maintained substantially free of any catalytic loading metal or metals, in accordance with a preferred embodiment of the present invention, by dispersing them in a slurry of the precursors of the siliceous gel matrix at a pH of 5 or above. When sodium forms of interstratified aluminosilicate and molecular sieve are starting materials, they may be converted to the ammonium or hydrogen form by ion exchange prior to being combined with the other catalyst components. Alternatively, they may be combined with the other catalyst components and then converted to the ammonium or hydrogen form by ion exchange. In either case, the interstratified aluminosilicate and molecular sieve components should not be combined with the precursors of the other catalyst components at a pH below 5, if catalytic metal loading is to be avoided.

D. Drying and Activation The catalyst following preparation in the aforesaid manner is dried in a conventional manner, and then desirably is activated in an oxygen-containing gas stream for 0.25 to 48 hours at 900 to 1,600F., preferably 0.25 to 48 hours at 900 to 1,300F. The oxygen-containing gas stream, which may be air, preferably is as dry as practicable. The improved results obtainable by activation in the indicated manner are optimized as the gas stream becomes extremely dry; although for most practical purposes the gas stream need be only as dry as ambientair, greater dryness is preferred. Those skilled in the art will be aware of various methods for drying the gas stream to any desired extent. B. Sulfiding The finished catalyst may be sulfided in a conventional manner prior to use, if desired. If not presulfided, the catalyst will tend to become sulfided during process operation from any sulfur content that may be present in the hydrocarbon feed.

OPERATION CONDITIONS The hydrocracking zone containing the catalyst of the present invention is operated at a temperature in the range 400 to 950F., preferably 500 to 850F., a pressure in the range 800 to 3,500 psig, preferably 1,000 to 3,000 psig, a liquid hourly space velocity in the range 0.1 to 5.0, preferably 0.5 to 5.0, and more preferably 0.5 to 3.0. The total hydrogen supply rate (makeup and recycle hydrogen) to said zone is 200 to 20,000 SCF, preferably 2,000 to 20,000 SCF of hydrogen per barrel of hydrocarbon feedstock.

The operating conditions in the reforming zone and catalytic cracking zone employed in various embodiments of the present invention are conventional conditions known in the art.

PROCESS OPERATION WITH REFERENCE TO DRAWING Referring now to FIG. 1 of the drawing, in accordance with one embodiment of the present invention, a hydrocarbon feedstock as previously described, which in this case may boil above 400F. and which may contain a substantial amount of organic nitrogen compounds, is passed through line 1 into hydrofininghydrocracking zone 2, which contains an embodiment of the catalyst of the present invention that includes a matrix comprising a silica-alumina gel, a component comprising manganese and a hydrogenating component comprising palladium. The feedstock is hydrocracked in hydrocracking zone 2 at conditions previously described, in the presence of hydrogen supplied through line 3. Under these conditions, concurrent hydrodenitrification takes place to the extent that the feedstock is substantially denitrified. The effluent from zone 2 is passed through line 4 to separation zone 5, from which hydrogen separated from the treated feedstock is recycled through line 6 to zone 2. In zone 5, water entering through line 7 is used to scrub ammonia and other contaminants from the incoming hydrocarbon stream, and the ammonia, water and other contaminants are withdrawn from zone 5 through line 8. From zone 5, the scrubbed, hydrocracked materials are passed through line 9 to distillation column 10, where they are separated into fractions, including a C fraction which is withdrawn through line 15, a C lF. fraction which is withdrawn through line 16, a l80-400F. fraction which is withdrawn through line 17, a 320550F. fraction which is withdrawn through line 18, and a 320 F.+ fraction which is withdrawn through line 19. The C l80F. fraction withdrawn through line 16 is a superior-quality light gasoline. The l80-400F. fraction withdrawn through line 17 is a superior catalytic reforming feedstock, which may be catalytically reformed in reforming zone 20, from which a superior catalytic reformate may be withdrawn through line 25. The 320-550F. fraction withdrawn through line 18 is a superior-quality jet fuel. The 320F.+ fraction withdrawn through line 19 is a superior hydrocracking feedstock, which may be catalytically hydrocracked in hydrocracking zone 26 in the presence of a conventional hydrocracking catalyst and in the presence of hydrogen supplied to zone 26 through line 27. From hydrocracking zone 26, an effluent may be withdrawn through line -28, hydrogen may be separated therefrom in separator 29, and hydrogen may be recycled to hydrocracking zone 26 through line 30. Alternatively, said 320F.+ fraction may be catalytically cracked in a catalytic cracking zone under conventional catalytic cracking conditions. From separator 29, hydrocracked materials may be passed through lines 35 and 9 to distillation column 10, where they may be separated into fractions, as previously described.

Referring now to FIG. 2, a hydrocarbon feedstock as previously described, which in this case may boil above 400F. and which may contain substantial amounts of organic nitrogen compounds, is passed through line 50 to hydrofining-hydrocracking zone 51, containing the same embodiment of the catalyst of the present invention as discussed in connection with FIG. 1. The feedstock is concurrently hydrofined and hydrocracked in zone 51 at conditions previously described in the presence of hydrogen supplied through line 52. The effluent from zone 51 may be passed through line 53 into hydrocracking zone 54, where it may be hydrocracked under the same conditions as used in zone 51, in the presence of a hydrocracking catalyst. The hydrocracking catalyst in zone 54 may be the same catalyst as used in zone 51, or may be a conventional hydrocracking catalyst comprising a crystalline zeolitic molecular sieve cracking component or a silica-alumina gel cracking component. lf the catalyst in zone 54 is the same catalyst as in zone 51, or if it comprises either an interstratified aluminosilicate cracking component or a crystalline zeolitic molecular sieve cracking component, rather than both of said components, the effluent from zone 51 may be passed through line 53 into zone 54 without intervening impurity removal. If the hydrocracking catalyst in zone 54 does not contain an interstratified aluminosilicate or a molecular sieve component, it is preferred that interstage removal of ammonia and other impurities be accomplished between zones 51 and 54. Zones 51 and 54 may be located in separate reactor shells, which may be operated at different pressures. Alternatively, zones 51 and 54 may be separate catalyst beds located in a single pressure shell 55, and the effluent from zone 51 may be passed to zone 54 without intervening pressure letdown, condensation or impurity removal, particularly in the case where zone 54 contains the catalyst of the present invention or a conventional catalyst comprising a crystalline zeolitic molecular sieve component. The effluent from zone 54 is passed through line 56 to separation zone 57, from which hydrogen is recycled through line 58 to hydrofining-hydrocracking zone 51. All or a portion of the recycled hydrogen may be passed through line 59 to hydrocracking zone 54, if desired. In separation zone 57, water entering through line 60 is used to scrub ammonia and other contaminants from the incoming hydrocarbon stream, if these contaminants previously have not been removed between zones 51 and 54, and the ammonia, water and other contaminants are withdrawn from zone 57 through line 65. The effluent from zone 57 is passed through line 66 to distillation column 67, where it is separated into fractions, including a C fraction which is withdrawn through line 68, a C l8OF. fraction which is withdrawn through line 69, a l-400F. fraction which is withdrawn through line 70, a 320-55 0F. fraction which is withdrawn through line 71, and a 32OF.+1r fraction which is withdrawn through line 72. The fraction withdrawn through line 72 may be recycled through lines 73 and 74 to hydrofininghydrocracking zone 51, and this is a preferred manner of operation. All or a portion of the fraction in line 73 may be recycled to hydrocracking zone 54 through line 75, if desired. The C -F. fraction withdrawn through line 69 is a superior-quality light gasoline. The l80-400F. fraction withdrawn through line 70 is a superior catalytic reforming feedstock, which may be catalytically reformed in reforming zone 76, from which a superior catalytic reformate may be withdrawn through line 77. The 320550F. fraction Withdrawn through line 71 is a superior-quality jet fuel. All or a portion of the 320F.+ fraction withdrawn through line 72 may be passed through line 78 to catalytic cracking zone 79, where it may be catalytically cracked under conventional catalytic cracking conditions in the presence of a conventional catalytic cracking catalyst to produce valuable fuel products, which may be withdrawn from zone 79 through line 80.

EXAMPLES The following examples are given for the purpose of further illustrating the catalyst of the present invention, the preparation thereof, and the use thereof in the process of the present invention. The examples are not intended to limit the scope of the present invention.

EXAMPLE 1 A catalyst consisting of manganese, palladium, and an interstratified clay-type smectite-illite crystalline aluminosilicate (Catalyst A, a comparison catalyst) was prepared in the following manner:

These starting materials were used:

1. 500 grams of an interstratified synthetic crystalline aluminosilicate mineral as described in Granquist US. Pat. No. 3,252,757;

2. An aqueous solution containing 1,250 cc. water and sufficient tetra ammino palladium dinitrate [Pd(NH )B4](NO and manganese nitrate [Mn(NO )B2] solution to produce a finished catalyst containing 0.5 percent of each metal, based on the interstratified aluminosilicate mineral.

The mineral, in powder form, was mixed with the aqueous solution to form a pasty mass. The pasty mass was dried and calcined at 950F. in flowing air. The calcined catalyst contained 0.5 weight percent palladium, calculated as the metal and based on the cracking component, and contained 0.5 percent manganese, calculated as metal and based on the cracking component.

13 EXAMPLE 2 A commercial catalyst consisting of 0.5 weight percent palladium on a crystalline zeolitic molecular sieve was calcined at 950F. in flowing air (Catalyst B, a comparison catalyst).

EXAMPLE 3 A catalyst consisting of: (a) an interstratified layered clay-type crystalline aluminosilicate mineral loaded with manganese and palladium; and (b) a crystalline zeolitic molecular sieve substantially free of hydrogenating metals (Catalyst C, a catalyst of the present invention) was prepared in the following manner.

These starting materials were used:

1. 500 grams of an interstratified synthetic crystalline aluminosilicate mineral as described in Granquist U.S. Pat. No. 3,252,757;

. An aqueous solution containing 1,250 cc. water and sufficient tetra ammino palladium dinitrate [Pd(Nl-l )B4](NO and manganese nitrate [Mn(NO )B2] solution to produce a finished catalyst containing 0.5 percent of each metal, based on the aluminosilicate mineral;

3. 75 grams of a low-sodium crystalline zeolitic molecular sieve.

The clay-type mineral, in powder form, was mixed with the aqueous solution to form a pasty mass. The pasty mass was dried and crushed to a powder. This dried powder was thoroughly mixed with the dry zeolitic molecular sieve. This final composite was tabletted and calcined in flowing air at 950F. The calcined catalyst contained 0.5 weight percent palladium, calculated as the metal and based on the clay-type mineral, and contained 0.5 weight percent manganese, calculated as the metal and based on the clay-type mineral.

EXAMPLE 4 Catalysts A, B and C of Examples 1,2 and 3, respectively, were used separately to hydrocrack separate portions of a light cycle oil feedstock of the following description:

Gravity, AP1 27.6 Aniline Point, F. 100.1 Nitrogen Content, ppm. 0.16 Boiling Range, F. 400-700 Catalyst Catalyst B C TEST 1 Liquid Hourly Space Velocity Conversion below 400F. 80%

Activity, F. Fouling Rate, F./hr. TEST 2 Liquid Hourly Space Velocity Conversion below 400F. 80%

Activity, F. Fouling Rate, F./hr.

TEST 3 Liquid Hourly Space Velocity Conversion below 400F. 80%

Activity, F.

Fouling Rate, F./hr.

In the above table, the numbers in brackets represent estimates of the catalyst performance from additional data and interpolations. The precise level of these estimates is not highly important, as the advantages of the catalyst of the present invention would be apparent even without these estimates.

The results of Test 1 are indeed surprising. Catalyst A, a palladium-managanese-clay catalyst, exhibited excellent activity, but only marginal stability. Catalyst B, a palladium-on-zeolite catalyst, exhibited a poor activity, but high stability. However, Catalyst C,a palladiummanganese-clay catalyst containing 15 percent unloaded zeolite, exhibited an activity surpassing both catalysts and an excellent stability.

Test 2 demonstrates that Catalyst A has very poor stability at high space velocities. It is surprising that such a component, constituting percent of Catalyst C, can survive the high severity conditions of Tests 3 and 4.

1n Tests 3 and 4, the unusually high stability and activity of Catalyst C is demonstrated at high severities. Catalyst C is 40F. more active than Catalyst B, 'a metal-loaded sieve catalyst; is 18F. more active that Catalyst A, a metal-loaded clya catalyst; is of equal stability to Catalyst B; and is orders of magnitude more stable than Catalyst A.

Catalyst C represents a case wherein a favorable synergism must exist between the unloaded zeolitic molecular sieve and the metal-loaded clay. Such a synergism is impossible to predict, an is particularly surprising in that a metal-free component would be expected to foul rapidly (or Catalyst C would be expected to be the least stable catalyst) and a mixture of these components is more active than the individual metalloaded components.

What is claimed is:

1. A hydrocarbon conversion catalyst comprising an interstratified smectite-illite crystalline clay-type aluminosilicate component, a crystalline zeolitic molecular sieve component, a hydrogenating component selected from platinum and compounds thereof and palladium and compounds thereof, and a component selected from the metals cerium, manganese, zinc, and compounds of said metals.

2. A catalyst as in claim 1, wherein one of said crystalline components is substantially in the ammonium or hydrogen form, and further is substantially free of any catalytic loading metal or metals.

3. A catalyst as in claim 1, wherein said interstratified crystalline component contains 00.5 weight percent sodium and 0.0-3.0 weight percent fluorine, all on an anhydrous interstratified crystalline component basis.

4. A catalyst as in claim 1, which further comprises a component selected from .the metals Ag, Cu, Sn, Ti, Zr, Th, Hf, V, alkaline earth metals Mg, Ca, Sr and Ba, rare earth metals having atomic numbers 57 and 59-71, and compounds of said metals.

5. A catalyst as in claim 1, wherein said interstratified crystalline aluminosilicate component and said crystalline molecular sieve component are in particulate form and are dispersed in a matrix comprising a siliceous gel and said hydrogenating component.

6. A catalyst as in claim 5, wherein at least one of said crystalline components is substantially in the ammonium or hydrogen form, and further is substantially free of any catalytic loading metal or metals.

7. A catalyst as in claim 5, which further comprises tin or a compound thereof.

8. A hydrocarbon conversion catalyst comprising:

a. a gel matrix comprising a silica-alumina gel,

b. a hydrogenating component selected from platinum and compounds thereof and palladium and compounds thereof,

c. a component selected from the metals cerium, manganese, zinc, and compounds of said metals,

' d. an interstratified smectite-illite crystalline claytype aluminosilicate component in particulate form, and

e. a crystalline zeolitic molecular sieve component in particulate form; said interstratified aluminosilicate component and said molecular sieve component being dispersed through said gel matrix.

9. A catalyst as in claim 8, wherein said matrix further comprises combined fluorine, in an amount of 0.0 to 5.0 weight percent.

10. A catalyst composite comprising:

A. A gel matrix comprising:

a. -85 weight percent silica,

b. -94 weight percent alumina,

c. a platinum or palladium component, in the form of metal, oxide, sulfide or any combination thereof, in an amount of 0.01 to 3 weight percent of said matrix, calculated as metal,

. a component selected from cerium, manganese and zinc, in the form of metal, oxide, sulfide or any combination thereof, in an amount of 0.1 to 25 weight percent of said matrix, calculated as metal;

B. An interstratified smectite-illite crystalline claytype aluminosilicate in particulate form, dispersed through said matrix;

C. A crystalline zeolitic molecular sieve, in particulate form, dispersed through said matrix.

11. A catalyst composite as in claim 10, wherein said interstratified crystalline aluminosilicate is present in an amount of 5 to'99 weight percent, and said molecular sieve is present in an amount of l to 70 weight percent, based on said composite.

12. A catalyst composite as in claim 10, wherein at least one of said crystalline components is substantially in the ammonium or hydrogen form, and is substantially free of any catalytic loading metal or metals.

13. A catalyst composite as in claim 8, further comprising a component selected from the metals Ag, Cu, Sn, Ti, Zr, Th, Hf, V, alkaline earth metals Mg, Ca, Sr and Ba, rare earth metals having atomic numbers 57 and 59-71, and compounds of said metals.

14. A catalyst composite as in claim 13, comprising titanium in the form of titania.

15. A catalyst composite as in claim. 10, characterized by an average pore diameter below 100 Angstroms and a surface area above 200 square meters per gram.

16. A catalyst consisting essentially of:

A. A orous xerogel comprising:

a. to weight percent silica,

b. 10 to 94 weight percent alumina,

c. palladium, in the form of metal, oxide, sulfide, or any combination thereof, in an amount of 0.01 to 3 weight percent of said Xerogel, calculated as metal,

d.'a component selected from cerium manganese and zinc, in the form of metal, oxide, sulfide or --any combination thereof, in an amount of 5 to 25 weight percent of said xerogel, calculated as metal,

e. titanium oxide, in an amount of 0.1 to 10 weight percent of said xerogel, calculated as metal;

B. A clay-type, interstratified smectite-illite crystalline aluminosilicate, in an amount of 5 to 99 weight percent of said catalyst, said crystalline alumunosilicate being in the form of particles, said particles being dispersed through said xerogel;

C. A crystalline zeolitic molecular sieve, in an amount of l to 70 weight percent of said catalyst, said molecular sieve being in the form of particles, said particles being dispersed through said xerogel; said catalyst having an average pore diameter below 100 Angstroms and a surface area above 200 square meters per gram.

17. A hydrotreating process which comprises contacting a hydrocarbon feed containing substantial amounts of materials boiling above 200F. and selected from the group consisting of petroleum distillates, solvent-deasphalted petroleum residua, shale oils and coal tar distillates, in a reaction zone with hydrogen and the catalyst of claim 1, at hydrotreating conditions including a temperature in the range 400 to 950F., a pressure in the range 800 to 3,500 psig, a liquid hourly space velocity in the range 0.1 to 5.0, and a total hydrogen supply rate of 200 to 20,000 SCF of hydrogen per barrel of feedstock, and recovering hydrotreated products from said reaction zone.

18. A process as in claim 17, wherein said hydrocarbon feed contains a substantial amount of organic nitrogen, and wherein ammonia is removed from the effluent from said reaction zone.

19. A process as in claim 17, wherein a gasoline product and a jet fuel product are recovered from the effluent from said reaction zone.

20. A process as in claim 19, wherein a portion of the effluent from said reaction zone boiling above the gasoline boiling range is hydrocracked in a second reaction zone in the presence of hydrogen and a hydrocracking catalyst at hydrocracking conditions including a temperature in the range 400 to 950F., a pressure in the range 800 to 3,500 psig, a liquid hourly space velocity in the range 0.1 to 5.0, and a total hydrogen supply rate of 200 to 20,000 SCF of hydrogen per barrel of feedstock, and wherein at least one hydrocracked product is recovered from said reaction zone. 

1. A hydrocarbon conversion catalyst comprising an interstratified smectite-illite crystalline clay-type aluminosilicate component, a crystalline zeolitic molecular sieve component, a hydrogenating component selected from platinum and compounds thereof and palladium and compounds thereof, and a component selected from the metals cerium, manganese, zinc, and compounds of said metals.
 2. A catalyst as in claim 1, wherein one of said crystalline components is substantially in the ammonium or hydrogen form, and further is substantially free of any catalytic loading metal or metals.
 3. A catalyst as in claim 1, wherein said interstratified crystalline component contains 0-0.5 weight percent sodium and 0.0-3.0 weight percent fluorine, all on an anhydrous interstratified crystalline component basis.
 4. A catalyst as in claim 1, which further comprises a component selected from the metals Ag, Cu, Sn, Ti, Zr, Th, Hf, V, alkaline earth metals Mg, Ca, Sr and Ba, rare earth metals having atomic numbers 57 and 59-71, and compounds of said metals.
 5. A catalyst as in claim 1, wherein said interstratified crystalline aluminosilicate component and said crystalline molecular sieve component are in particulate form and are dispersed in a matrix comprising a siliceous gel and said hydrogenating component.
 6. A catalyst as in claim 5, wherein at least one of said crystalline components is substantially in the ammonium or hydrogen form, and further is substantially free of any catalytic loading metal or metals.
 7. A catalyst as in claim 5, which further comprises tin or a compound thereof.
 8. A hydrocarbon conversion catalyst comprising: a. a gel matrix comprising a silica-alumina gel, b. a hydrogenating component selected from platinum and compounds thereof and palladium and compounds thereof, c. a component selected from the metals cerium, manganese, zinc, and compounds of said metals, d. an interstratified smectite-illite crystalline clay-type aluminosilicate component in particulate form, and e. a crystalline zeolitic molecular sieve component in particulate form; said interstratified aluminosilicate component and said molecular sieve component being dispersed through said gel matrix.
 9. A catalyst as in claim 8, wherein said matrix further comprises combined fluorine, in an amount of 0.0 to 5.0 weight percent.
 10. A catalyst composite comprising: A. A gel matrix comprising: a. 5-85 weight percent silica, b. 10-94 weight percent alumina, c. a platinum or palladium component, in the form of metal, oxide, sulfide or any combination thereof, in an amount of 0.01 to 3 weight percent of said matrix, calculated as metal, d. a component selected from cerium, manganese and zinc, in the form of metal, oxide, sulfide or any combination thereof, in an amount of 0.1 to 25 weight percent of said matrix, calculated as metal; B. An interstratified smectite-illite crystalline clay-type aluminosilicate in particulate form, dispersed through said matrix; C. A crystalline zeolitic molecular sieve, in particulate form, dispersed through said matrix.
 11. A catalyst composite as in claim 10, wherein said interstratified crystalline aluminosilicate is present in an amount of 5 to 99 weight percent, and said molecular sieve is present in an amount of 1 to 70 weight percent, based on said composite.
 12. A catalyst composite as in claim 10, wherein at least one of said crystalline components is substantially in the ammonium or hydrogen form, and is substantially free of any catalytic loading metal or metals.
 13. A catalyst composite as in claim 8, further comprising a component selected from the metals Ag, Cu, Sn, Ti, Zr, Th, Hf, V, alkaline earth metals Mg, Ca, Sr and Ba, rare earth metals having atomic numbers 57 and 59-71, and compounds of said metals.
 14. A catalyst composite as in claim 13, comprising titanium in the form of titania.
 15. A catalyst composite as in claim 10, characterized by an average pore diameter below 100 Angstroms and a surface area above 200 square meters per gram.
 16. A catalyst consisting essentially of: A. A porous xerogel comprising: a. 5 to 85 weight percent silica, b. 10 to 94 weight percent alumina, c. palladium, in the form of metal, oxide, sulfide, or any combination thereof, in an amount of 0.01 to 3 weight percent of said xerogel, calculated as metal, d. a component selected from cerium manganese and zinc, in the form of metal, oxide, sulfide or any combination thereof, in an amount of 5 to 25 weight percent of said xerogel, calculated as metal, e. titanium oxide, in an amount of 0.1 to 10 weight percent of said xerogel, calculated as metal; B. A clay-type, interstratified smectite-illite crystalline aluminosilicate, in an amount of 5 to 99 weight percent of said catalyst, said crystalline alumunosilicate being in the form of particles, said particles being dispersed through said xerogel; C. A crystalline zeolitic molecular sieve, in an amount of 1 to 70 weight percent of said catalyst, said molecular sieve being in the form Of particles, said particles being dispersed through said xerogel; said catalyst having an average pore diameter below 100 Angstroms and a surface area above 200 square meters per gram.
 17. A hydrotreating process which comprises contacting a hydrocarbon feed containing substantial amounts of materials boiling above 200*F. and selected from the group consisting of petroleum distillates, solvent-deasphalted petroleum residua, shale oils and coal tar distillates, in a reaction zone with hydrogen and the catalyst of claim 1, at hydrotreating conditions including a temperature in the range 400* to 950*F., a pressure in the range 800 to 3,500 psig, a liquid hourly space velocity in the range 0.1 to 5.0, and a total hydrogen supply rate of 200 to 20,000 SCF of hydrogen per barrel of feedstock, and recovering hydrotreated products from said reaction zone.
 18. A process as in claim 17, wherein said hydrocarbon feed contains a substantial amount of organic nitrogen, and wherein ammonia is removed from the effluent from said reaction zone.
 19. A process as in claim 17, wherein a gasoline product and a jet fuel product are recovered from the effluent from said reaction zone. 